• Title/Summary/Keyword: Competitive Kinetics

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Kinetics and Mechanism of Nucleophilic Addition of Sodium Thiophenoxide to $\alpha$-(n-Butyl)-N-Phenylnitrone Derivatives ($\alpha$-(n-Butyl)-N-Phenylnitrone 유도체에 대한 Sodium Thiophenoxide의 친핵성 첨가반응 메카니즘과 그의 반응 속도론적 연구)

  • Lee, Gwang Il;Lee, Seok U;Gwak, Cheon Geun;Kim, Yeong Ju;No, Seung Il;Lee, Gi Chang
    • Journal of the Korean Chemical Society
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    • v.38 no.6
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    • pp.442-448
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    • 1994
  • The rate constants of the nucleophilic reaction of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by ultraviolet spectrophotometry at $25^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. Final product of the addition reaction was $\alpha$-phenylthiobutylidene-aniline. Base on the rate equation, genernal base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0 the reaction was inititated by the addition of thiophenol, and in the range of pH 3.0∼10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

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The Kinetics and Mechanism of Nucleophilic Addition of n-Propylmercaptan to $\alpha$-Cyano-$\beta$-piperonylacrylic Acid ($\alpha$-Cyano-$\beta$-piperonylacrylic Acid에 대한 n-Propylmercaptan의 친핵성 첨가반응에 관한 연구)

  • Kim, Tae-Rin;Huh, Tae-Seong
    • Journal of the Korean Chemical Society
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    • v.17 no.5
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    • pp.363-370
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    • 1973
  • The rate constants of the nucleophilic addition of n-propyl-mercaptan to $\alpha$-cyano-$\beta$-piperonylacrylic acid were determined at various pH and a rate equation which can be applied over wide pH range is obtained. The rate equation reveals that below pH 4.5 the reaction is initiated by the attack of n-propylmercaptan to $\alpha$-cyano-$\beta$-piperonylacrylic acid. At pH 4.5~6.5, however, n-propylmercaptan is added to $\alpha$-cyano-$\beta$-piperonylacrylate ion; at pH 7.04~9.5 the competitive reaction between n-propylmercaptan and n-propylmercaptide ion is anticipated to occur. Above pH 10 the addendum is n-propylmercaptide ion and the acceptor is $\alpha$-cyano-$\beta$-piperonylacrylate ion.

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Characteristics of Lactose Hydrolysis by Immobilized β-Galactosidase on Chitosan Bead (Chitosan 담체에 고정화된 β-galactosidase에 의한 유당 분해 특성)

  • Kang, Byung-Chul
    • Journal of Life Science
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    • v.21 no.1
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    • pp.127-133
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    • 2011
  • ${\beta}$-Galactosidase was immobilized on chitosan bead by covalent bonding using glutaraldehyde. The characteristics of the immobilized enzyme were investigated. Maximum immobilization yield of 75% was obtained on chitosan bead. Optimum pH and temperature for the immobilized enzyme was 7.0 and $50^{\circ}C$, respectively. The immobilized enzyme showed a broader range of pH and temperature compared to a free one. A mathematical model for the operation of the immobilized enzyme in a packed-bed reactor was established and solved numerically. Under different inlet lactose concentrations and feed flow rate conditions, lactose conversion was measured in a packed-bed reactor. The experimental results of continuous operation in a packed-bed reactor were compared to theoretic results using Michaelis-Menten kinetics with competitive product inhibition and external mass transfer resistance. The model predicted the experimental data with errors less than 5%. Process optimization of continuous operation in a packed-bed reactor was also conducted. In a recirculation packed-bed operation, conversion of lactose was 97% in 3 hours. In a continuous packed-bed operation, the effect of flow rate and initial lactose concentration was investigated. Increasing flow rates and initial lactose concentration decreased the conversion of substrate.

Kinetic Analysis of Isocitrate lyase from Saccharomycopsis lipolytica (Saccharomycopsis lipolytica isocitrate lyase의 Kinetic 분석)

  • Cho, Seok-Gum;Chung, Dong-Hyo
    • Applied Biological Chemistry
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    • v.31 no.2
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    • pp.137-142
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    • 1988
  • The analysis of condensation and cleavage reaction was carried out at $30^{\circ}C$ and pH 7.0 with purified isocitrate lyase from Saccharomycopsis lipolytica ATCC 44601. The Km values for condensation reaction of glyoxylate and succinate were 0.06 and 0.21 mM, respectively. In the cleavage reaction, glyoxylate was a linear competitive inhibitor with a Ki of 0.22 mM and succinate was a linear noncompetitive inhibitor with a Ki of 0.82 mM. Therefore, these kinetic analyses showed that the enzyme functioned in a ordered reaction with glyoxylate binding before succinate in the condensation reaction. 3-Bromopyruvate(BrP) was found to be irreversibly inactivation showing saturation kinetics, the inactivation half-time was 0.15 min and $K_{BrP}$ was 0.032 mM, and substrate or reactant protected against the inactivation.

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Reduction of Perchlorate and Nitrate by Citrobacter Amalonaticus Strain JB101 : Kinetics and the Applicability of MBR (Citrobacter Amalonaticus Strain JB101에 의한 과염소산염과 질산염의 환원 : Kinetics 및 MBR을 이용한 처리 가능성)

  • Hong, Jae-Wha;Jang, Myung-Su;Lee, Il-Su;Bae, Jae-Ho
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.12
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    • pp.1298-1304
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    • 2005
  • This study was performed to evaluate the characteristics of the competition between two electron acceptors, perchlorate and nitrate, with Citrobacter Amalonaticus strain JB101. In addition, the applicability of membrane bioreactor(MBR) for perchlorate removal was evaluated. The maximum growth rate of strain JB101 on perchlorate and nitrate are 0.27 and 0.58 $hr^{-1}$, and maximum substrate utilization rates were 35.1 mg $ClO_4^-/g$ protein-day and 45.6 mg $NO_3^-/g$ protein-day, respectively. Nitrate was a competitive inhibitor for perchlorate, and strain JB101 prefer nitrate to perchlorate as electron acceptor. Complete removal of perchlorate could be achieved up to the surface leading rate of 4.6 g $ClO_4^-/m^2-day$ with the MBR fed with 20 mg $ClO_4^-/L$(HCMBR). When 5 mg/L of nitrate was added to the same influent, perchlorate removal efficiency decreased to 96.5%, while nitrate was completely removed. For the MBR fed with 0.7 mg/L of perchlorate (LCMBR), the maximum perchlorate removal efficiency was 100% up to the loading rate of 0.23 g $ClO_4^-/m^2-day$. Membrane fouling was found to be a problem at high leading rate for both MBRs. The acetate consumption ratio per perchlorate was $13.7{\sim}51.7\;e^-eq./e^-eq.$ in LCMBR, while the value was $2.5{\sim}3.6\;e^-eq./e^-eq.$ in HCMBR. This difference could be related to the acetate consumption with oxygen as electron acceptor. Therefore, the amount of acetate addition must be determined considering the concentrations of other electron acceptors in the influent.

Sorption and Ion Exchange Characteristics of Chabazite: Competition of Cs with Other Cations (차바자이트의 흡착 및 이온 교환 특성: Cs 및 다른 양이온과의 경쟁)

  • Baek, Woohyeon;Ha, Suhyeon;Hong, Sumin;Kim, Seonah;Kim, Yeongkyoo
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.2
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    • pp.59-71
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    • 2016
  • To investigate the sorption characteristics of Cs, which is one of the major isotopes of nuclear waste, on natural zeolite chabazite, XRD, EPMA, EC, pH, and ICP analysis were performed to obtain the informations on chemical composition, cation exchange capacity, sorption kinetics and isotherm of chabazite as well as competitive adsorption with other cations ($Li^+$, $Na^+$, $K^+$, $Rb^+$, $Sr^{2+}$). The chabazite used in this experiment has chemical composition of $Ca_{1.15}Na_{0.99}K_{1.20}Mg_{0.01}Ba_{0.16}Al_{4.79}Si_{7.21}O_{24}$ and its Si/Al ratio and cation exchange capacity (CEC) were 1.50 and 238.1 meq/100 g, respectively. Using the adsorption data at different times and concentrations, pseudo-second order and Freundlich isotherm equation were the most adequate ones for kinetic and isotherm models, indicating that there are multi sorption layers with more than two layers, and the sorption capacity was estimated by the derived constant from those equations. We also observed that equivalent molar fractions of Cs exchanged in chabazite were different depending on the ionic species from competitive ion exchange experiment. The selectivity sequence of Cs in chabazite with other cations in solution was in the order of $Na^+$, $Li^+$, $Sr^{2+}$, $K^+$ and $Rb^+$ which seems to be related to the hydrated diameters of those caions. When the exchange equilibrium relationship of Cs with other cations were plotted by Kielland plot, $Sr^{2+}$ showed the highest selectivity followed by $Na^+$, $Li^+$, $K^+$, $Rb^+$ and Cs showed positive values with all cations. Equilibrium constants from Kielland plot, which can explain thermodynamics and reaction kinetics for ionic exchange condition, suggest that chabazite has a higher preference for Cs in pores when it exists with $Sr^{2+}$ in solution, which is supposed to be due to the different hydration diameters of cations. Our rsults show that the high selectivity of Cs on chabazite can be used for the selective exchange of Cs in the water contaminated by radioactive nuclei.

Competitive Adsorption of Two Basic Dyes RB5 and GB4 on a Local Clay (점토에 대한 2개 염기성 염료 RB5와 GB4의 경쟁 흡착)

  • Elaziouti, A.;Derriche, Z.;Bouberka, Z.;Laouedj, N.
    • Journal of the Korean Chemical Society
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    • v.54 no.1
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    • pp.110-114
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    • 2010
  • The equilibrium of adsorption of basics dyes RB 5 and BG 4 from a single dyes in the mixtures on the sodium-exchanged clay of the Maghnia (Algeria) was studied. The maximum adsorption capacities of BR5 and BG4 in single dyes were 465.13 and 469.90 mg/g respectively. In the simultaneous adsorption of BR5 and BG4 from mixture solutions, three different initials concentrations ratios R (R=$C_{(BR5)}/C_{(BG4)}$) were tested: 2.5/1, 1/1 and 1/2.5 using ADMI method. The isotherms adsorptions of dyes from the mixtures are characteristics of competition phenomenon. A very strong interaction between BR5 and BG4 for the active sites of adsorption of surface of clay is obtained for R = 1/1. The ratio R' (R'=$Qe_{(mixture)}/Qe_{(single)}$) of the adsorption capacity of BR5 and BG4 in the mixture were reduced by factor of 0.86, 0.74 and 0.84 for the initials concentrations ratios R (R=$C_{(BR5)}/C_{(BG4)}$) of 2.5/1, 1/1 and 1/2.5 respectively. The variation of the ratio of the adsorption capacity R‘ of BR5 and BG4 in the mixture solutions with initial concentration ratios R indicates that BR5 dye is slightly favourable in the competition adsorption than BG4. Langmuir and Freundlich models fit very well with adsorption behaviour of single dyes as well as the dyes in mixture solutions.

Studies on Screening and Iolation of ${\alpha}-Amylase$ Inhibitors of Soil Microorganisms( II ) -Isolation and Activities of the Inhibitor of Streptomyces Strain DMC-72- (토양균의 ${\alpha}-Amylase$ 저해제 검색 및 분리에 관한 연주(제2보) -스트렙토마이세스속 DMC-72 균주의 저해 성분의 분리 및 작용-)

  • Kim, Kyung-Jae;Lee, Shung-Hee;Kim, Jung-Woo;Kim, Ha-Won;Shim, Mi-Ja;Choi, Eung-Chil;Kim, Byong-Kak
    • The Korean Journal of Mycology
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    • v.13 no.4
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    • pp.203-212
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    • 1985
  • Of 450 strains isolated from the soil microbes collected in various locations in Korea, a strain had a strong inhibitory activity against bacterial ${\alpha}-amylase$ and was named strain DMC-72 of the genus Streptomyces. The amylase inhibitory metabolite produced by this strain was purified by means of acetone precipitation, adsorption on Amberlite IRC-50 and SP-Sephadex C-25. The inhibitor was found to be a derivative of oligosaccharides by spectral and chemical data. The inhibitor was stable at the pH range of $1{\sim}13$ and at $100^{\circ}C$ for half an hour, also inhibited other amylases such as salivary ${\alpha}-amylase$, pancreatic ${\alpha}-amylase$, fungal ${\alpha}-amylase$ and glucoamylase. However, it showed no inhibitory activity against ${\alpha}-glucosidase$, ${\beta}-glucosidase$, dextranase, and ${\beta}-amylase$. The kinetic studies of the inhibitor showed that its inhibitory effects on starch hydrolysis by ${\alpha}-amylase$ were noncompetitive.

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The Inhibitory Effect of Cornus walteri Extract Against ${\alpha}-amylase$ (말채나무 추출물의 ${\alpha}-amylase$ 저해 활성)

  • Lim, Chae-Sung;Li, Chun-Ying;Kim, Yong-Mu;Lee, Wi-Young;Rhee, Hae-Ik
    • Applied Biological Chemistry
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    • v.48 no.1
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    • pp.103-108
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    • 2005
  • ${\alpha}-Amylase$ inhibitor is used to control blood glucose level by inhibiting starch digestion in the small intestine and delaying the absorption of glucose. In this study, we investigated the effect of the ethanol extracts from more than 1400 species of plants against ${\alpha}-amylase$ with the aim of developing a new ${\alpha}-amylase$ inhibitor. In the results, Cornus walteri extracts showed the highest inhibition activity. The inhibitory effect of Cornus walteri extract on the carbohydrate hydrolysis enzymes has different sensitivities against ${\alpha}-amylase$ from salivary and pancreatin and against ${\alpha}-glucosidase$ from yeast and porcine small intestine. In the study of inhibition kinetics of ${\alpha}-amylase$ and ${\alpha}-glucosidase$, Cornus walteri extract showed competitive inhibition against salivary and pancreatin while showing the combination of uncompetitive and noncompetitive inhibition against ${\alpha}-glucosidase$. The Cornus walteri extract was stable at acidic and thermal conditions. As for the blood glucose and body weight levels of Cornus walteri extract, we confirmed anti-hyperglycemic and anti-obesity effects. Also, in the investigation of the mRNA lever, Cornus walteri extract upregulated the level of GLUT4 mRNA in the quadriceps muscle.

Preparation of ZrC/SiC by Carbothermal Reduction of Zircon (지르콘의 탄소열환원에 의한 ZrC/SiC의 합성)

  • Park, Hong-Chae;Lee, Yoon-Bok;Lee, Cheol-Gyu;Oh, Ki-Dong
    • Applied Chemistry for Engineering
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    • v.5 no.6
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    • pp.1044-1055
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    • 1994
  • The preparation of ZrC/SiC mixed powders from $ZrSiO_4/C$ and $ZrSiO_4/Al/C$ systems was attempted in the temperature range below $1600^{\circ}C$ under Ar or $Ar/H_2$ gas flow(100-500ml/min). The formation mechanism and kinetics of ZrC/SiC were suggested and the resultant powders were characterized. In $ZrSiO_4/C$ system, ZrC and SiC were formed by competitive reaction of $ZrO_2(s)$ and SiO(g) with carbon at temperature higher than $1400^{\circ}C$. The apparent activation energy for the formation of ZrC was approximately 18.5kcal/mol($1400-1600^{\circ}C$). In $ZrSiO_4/Al/C$ system, ZrC was formed by reaction of ZrO(g) with Al(l, g) and carbon at temperature higher than $1200^{\circ}C$, and SiC was formed by reduction-carbonization of SiO(g) with Al(l, g) and carbon at temperature higher than $1300^{\circ}C$. The products obtained at $1600^{\circ}C$ for 5h consisted of ZrC with lattice constant of $4.679{\AA}$ and crystallite size of $640{\AA}$, and SiC with lattice constant of $4.135{\AA}$ and crystallize size of $500{\AA}$. And also, the mean particle size was about $21.8{\mu}m$.

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